Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B43/00—Preparation of azo dyes from other azo compounds
  • C09B43/12—Preparation of azo dyes from other azo compounds by acylation of amino groups
  • C09B43/136—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents
  • C09B43/16—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents linking amino-azo or cyanuric acid residues
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B56/00—Azo dyes containing other chromophoric systems
  • C09B56/04—Stilbene-azo dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
  • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
  • C09B62/08—Azo dyes
  • C09B62/082—Azo dyes dyes containing in the molecule at least one azo group and at least one other chromophore group
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/82—Textiles which contain different kinds of fibres
  • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
  • D06P3/8223—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups
  • D06P3/8228—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using one kind of dye
  • D06P3/8233—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using one kind of dye using dispersed dyes

Definitions

• the present invention relates to new azo dyes, processes for their preparation and their use for dyeing and printing fiber materials, in particular textile fiber materials.
• the object underlying the present invention was to find dyes which are suitable for dyeing nitrogen-containing and hydroxyl-containing fiber materials, in particular cellulosic fiber materials, have good fastness properties and are stable at high temperatures.
• the present invention thus relates to azo dyes of the formula wherein R1, R2, R3 and R4 independently of one another are hydrogen or optionally substituted C1-C4-alkyl, R5 and R6 independently of one another are hydrogen, halogen, optionally substituted by hydroxy-substituted C1-C4-alkyl or C1-C4-alkoxy, unsubstituted or substituted in the alkyl part by hydroxy or C1-C4-alkoxy C2-C4-alkanoylamino or unsubstituted or ureido mono- or disubstituted by C1-Cido-alkyl in the terminal amino group, Y1 and Y2 independently of one another amino, unsubstituted or substituted in the alkyl part by hydroxy, sulfo, carboxy or C1-C4-alkoxy N-mono- or N, N-di-C1-C4-alkylamino, unsubstit
• R1, R2, R3, R4, R5 and R6 e.g. Methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl or isobutyl, especially methyl or ethyl, preferably methyl, into consideration.
• Possible substituents of the radicals R1, R2, R3 and R4 as C1-C4-alkyl are e.g. Hydroxy, C1-C4 alkoxy, halogen or sulfato called.
• the radicals R5 and R6 as C1-C4-alkyl may be further substituted by hydroxy.
• the meaning sulfo generally includes the free acid form (-SO3H) as well as the salt form, alkali metal salts (Li, Na, K) or ammonium salts being particularly suitable.
• R5 and R6 are, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, especially methoxy.
• the radicals R5 and R6 as C1-C4-alkoxy can be further substituted by hydroxy.
• R5 and R6 e.g. Fluorine or chlorine, especially chlorine, into consideration.
• C2-C4-alkanoylamino for R5 and R6 are both the unsubstituted and in the alkyl part substituted by hydroxy or C1-C4-alkoxy into consideration.
• the unsubstituted radicals such as e.g. Acetylamino or propionylamino.
• Examples of substituted radicals are -NH-CO-CH2-OH and -NH-CO-CH2-OCH3.
• C1-C4-alkyl substituted ureido are suitable for R5 and R6, for example, -NH-CO-NH2, NH-CO-NH-CH3 and NH-CO-N (CH3) 2.
• Y1 and Y2 as N-mono- or N, N-di-C1-C4-alkylamino can include both the unsubstituted and those in the alkyl part substituted by hydroxy, sulfo, carboxy or C1-C4-alkoxy.
• the radicals which are unsubstituted in the alkyl part and in particular those which are substituted by hydroxy in the alkyl part are preferred. Examples include N- ⁇ -hydroxyethylamino and N, N-di- ⁇ -hydroxyethylamino.
• Y1 and Y2 as C5-C7-cycloalkylamino can both the unsubstituted and those in the cycloalkyl ring by C1-C4-alkyl, such as e.g. Include methyl or ethyl, especially methyl, substituted groups.
• C1-C4-alkyl such as e.g. Include methyl or ethyl, especially methyl, substituted groups.
• the corresponding cyclohexyl radicals are preferred as such radicals.
• Y1 and Y2 as phenylamino or N-C1-C4-alkyl-N-phenylamino is preferably phenylamino. These radicals are preferably unsubstituted in the phenyl ring.
• A1 and A2 in the meaning of phenyl or naphthyl can be unsubstituted or substituted, for example, by C1-C4-alkyl, C1-C4-alkoxy, C2-C4-alkanoylamino, ureido, halogen, carboxy or sulfo.
• the sulfo-substituted radicals are of particular importance here.
• R1, R2, R3 and R4 are preferably hydrogen or C1-C4-alkyl, especially hydrogen.
• R5 and R6 are preferably independently of one another unsubstituted or substituted in the alkyl part by hydroxy or C1-C4-alkoxy C2-C4-alkanoylamino or unsubstituted or in the terminal amino group mono- or disubstituted by C1-C U-alkyl ureido.
• R5 and R6 are particularly preferably C2-C4-alkanoylamino or ureido, in particular C2-C4-alkanoylamino and preferably acetylamino.
• A1 and A2 are preferably independently of one another optionally phenyl substituted by C1-C4-alkyl, C1-C4-alkoxy, C2-C4-alkanoylamino, ureido, halogen, carboxy or sulfo or naphthyl optionally substituted by sulfo, in particular phenyl optionally substituted by C1-C4-alkyl, C1-C4-alkoxy, C2-C4-alkanoylamino, ureido, halogen, carboxy or sulfo, and preferably phenyl substituted by sulfo.
• radicals A1 and A2 are preferably identical.
• Y1 and Y2 are preferably independently of one another amino, unsubstituted or in the alkyl part substituted by hydroxy N-mono- or N, N-di-C1-C4-alkylamino, cyclohexylamino, phenylamino, morpholino or piperidin-1-yl.
• Y1 and Y2 are particularly preferably independently of one another in the alkyl part substituted by hydroxy N-mono- or N, N-di-C1-C4-alkylamino or morpholino, in particular N- ⁇ -hydroxyethylamino, N, N-N-di- ⁇ -hydroxyethylamino or morpholino and preferably morpholino.
• radicals Y1 and Y2 are preferably identical.
• azo dyes of the formula (1) in which R1, R2, R3 and R4 are hydrogen, R6 and R6 independently of one another are unsubstituted or in the alkyl part substituted by hydroxy or C1-C4alkoxy C2-C4alkanoylamino or unsubstituted or in the terminal amino group Ureido substituted once or twice by C1-C4-alkyl, Y1 and Y2 independently of one another are amino, unsubstituted or in the alkyl part substituted by hydroxy N-mono- or N, N-di-C1-C4-alkylamino, cyclohexylamino, phenylamino, morpholino or piperidin-1-yl, and A1 and A2 independently of one another are optionally substituted by C1-C4-alkyl, C1-C4-alkoxy, C2-C4-alkanoylamino, ureido, halogen
• the radicals A1 and A2 and the Residues Y1 and Y2 each have identical meanings.
• Azo dyes of the formula (1) are very particularly preferred in which R6 and R6 are C2-C4-alkanoylamino, Y1 and Y2 are morpholino and A1 and A2 are phenyl substituted by sulfo.
• the radicals A1 and A2 have identical meanings.
• the trihalogenotriazine compound of the formula (2) is initially set with approximately stoichiometric amounts of an aminoazo compound of the formula (3) or of the formula (5) at a temperature of e.g. -5 to 20 ° C, preferably 0 to 5 ° C, the pH being adjusted by adding suitable bases, e.g. Alkali metal bases such as lithium, sodium or potassium hydroxide or carbonate or bicarbonate, neutral to acidic, preferably at 2 to 7, in particular 3 to 5, is kept.
• suitable bases e.g. Alkali metal bases such as lithium, sodium or potassium hydroxide or carbonate or bicarbonate
• the aminoazo compound of the formula (3) or of the formula (5) is expediently used in approximately stoichiometric amounts.
• the reaction of the compound of formula (7) in succession with the compounds of formulas (4) and (6) obtained in a) is preferably carried out at a temperature of e.g. 10 to 50 ° C, especially 20 to 40 ° C, and a neutral to acidic pH, e.g. 3 to 7, in particular 4 to 6, is carried out, expediently using approximately stoichiometric amounts of the compounds (4), (6) and (7).
• a temperature e.g. 10 to 50 ° C, especially 20 to 40 ° C
• a neutral to acidic pH e.g. 3 to 7, in particular 4 to 6
• the triazinyl dyes of the formula (8) which can be obtained by the processes described above also contain halogen atoms Z which, by reaction with at least one compound of the formulas (9) and (10) at elevated temperature, preferably 70 to 100 ° C., and a neutral to slightly alkaline pH, which, depending on the compound of formula (9) or (10) used, for example 7 to 12, especially 8 to 12, can be converted into a group Y1 or Y2.
• the compounds of the formulas (3) and (5) can be prepared in a known manner by diazotization and coupling of corresponding starting compounds are obtained, the diazotization in a manner known per se, for example with a nitrite, for example with an alkali metal nitrite such as sodium nitrite, in a mineral acid medium, for example in a hydrochloric acid medium, at temperatures of, for example, -5 to 40 ° C. and preferably at -5 to 10 ° C.
• the coupling takes place in a manner known per se, at acidic, neutral to weakly alkaline pH values and temperatures of, for example, 0 to 30 ° C.
• the azo dyes of the formula (1) are either in the form of their free acid or, preferably, as their salts.
• suitable salts are the alkali, alkaline earth or ammonium salts or the salts of an organic amine.
• suitable salts include the sodium, lithium, potassium or ammonium salts or the salt of mono-, di- or triethanolamine.
• Another object of the present invention is the use of the azo dyes of the formula (1) for dyeing or printing nitrogen-containing and in particular hydroxyl-containing fiber materials.
• the azo dyes of the formula (1) according to the invention are therefore suitable for dyeing and printing nitrogen-containing or, in particular, cellulosic fiber materials, preferably textile fiber materials, made from silk, wool or synthetic polyamides, and preferably from cellulosic fibers such as rayon, cotton or hemp.
• direct dyes C.I. direct dyes
• Textile fiber materials made from mixed fibers e.g. wool / cotton, polyamide / cotton, polyacrylic / cotton or in particular polyester / cotton mixed fibers can be dyed by a single bath dyeing process and in the presence of dyes for the other types of fibers.
• the textile fiber materials can be in a wide variety of processing states, such as fiber, yarn, woven or knitted fabric.
• leather and paper can also be dyed with azo dyes of the formula (1) according to the invention.
• Level dyeings are obtained in yellow shades with good general fastness properties, in particular good rub, wet, wet rub, sweat and light fastness. If necessary, the wet fastness properties, in particular the wash fastness, of the direct dyeings and prints obtained can be significantly improved by post-treatment with so-called fixing agents.
• the dyes of the formula (1) according to the invention can be easily combined with other dyes, in particular disperse dyes.
• the dyes according to the invention have sufficient high-temperature stability and can thus be used under the dyeing conditions for polyester fibers, i.e. dye at temperatures in the range from about 100 to 150 ° C., preferably from 110 to 130 ° C., from an aqueous liquor and at a pH of 4 to 7.5, preferably 5 to 7.
• the dyeing of textile mixed fibers e.g. simplify those made of polyester and cellulose fibers.
• the usual dyeing of each type of fiber in a fiber blend in a separate operation using different dyeing conditions is no longer necessary.
• Parts and percentages are by weight unless otherwise specified. Parts by weight and parts by volume are related in the same way as kilograms and liters. The temperatures are given in degrees Celsius.
• cyanuric chloride 19.4 parts are stirred with 100 parts of ice water and 100 parts of ice.
• the cyanuric chloride suspension obtained is initially charged and a solution of 33.4 parts of the compound of the formula (101) according to Example 1 in 750 parts of water is at a temperature of 0 to 2 ° C and a pH of 3.5 to 4 within dropped from 60 minutes.
• the pH is kept at a value of 3.5 to 4 by adding a 1 normal aqueous sodium hydroxide solution.
• the mixture obtained is left to react for about 2.5 hours.
• the consumption of 1-normal aqueous sodium hydroxide solution is approx. 110 parts.
• a reaction solution is obtained which is the compound of the formula given in the form of the free acid contains.
• 10 parts of a fiber mixture of polyester and cotton are placed at about 50 ° C in a dye bath which contains 200 parts of water, a dye mixture consisting of 0.2 parts of C.I. Disperse Yellow 99 and 0.2 parts of the dye according to Example 2, 0.4 parts of ammonium sulfate and 0.2 parts of an anionic dispersant (e.g. formaldehyde condensation product of naphthalenesulfonic acid).
• the dyebath is adjusted to a pH of 5.5 with formic acid, 1 part of sodium sulfate is added and the mixture is then heated to about 130 ° C. within 45 minutes. It is dyed for a further 45 minutes at 130 ° C., then the dyebath is cooled to about 80 ° C. within 30 minutes and left at this temperature for a further 45 minutes.
• the stain is then rinsed thoroughly with cold water and dried.
• the procedure is as described in dyeing instructions 1 or 2, but after the dyeing process is complete, the cold-rinsed dyeing is placed in a fresh bath at about 30 ° C. which contains 200 parts of water and 0.2-0.6 parts of a cationic aftertreatment agent (amine -Formaldehyde-dicyandiamide condensation product or preparation based on dicyandiamide and diethylenetriamine).
• a cationic aftertreatment agent amine -Formaldehyde-dicyandiamide condensation product or preparation based on dicyandiamide and diethylenetriamine.
• the procedure is as described in dyeing instructions 1 or 2, but after the dyeing process has ended, the cold-rinsed dyeing is placed in a fresh bath at about 25 ° C. which contains 200 parts of water, 1 part of sodium sulfate and 0.6 part of a fiber-reactive cationic aftertreatment agent Contains base of N-methyldialkylamine and epichlorohydrin.
• the temperature is raised to 40 ° C. in the course of 15 minutes, 0.8 part of 30% sodium hydroxide solution is added and the dyeing is treated at 40 ° C. for a further 45 minutes.
• the dyeing is then rinsed hot and dried; it has improved wet fastness properties.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Coloring (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=4222390

Family Applications (1)

Country Status (9)

Families Citing this family (4)

Citations (3)

Family Cites Families (3)

• 1995
  • 1995-06-02 US US08/460,176 patent/US5554734A/en not_active Expired - Fee Related
  • 1995-06-06 TW TW084105649A patent/TW279888B/zh active
  • 1995-06-13 ES ES95810393T patent/ES2123936T3/es not_active Expired - Lifetime
  • 1995-06-13 JP JP7146283A patent/JPH083465A/ja active Pending
  • 1995-06-13 DE DE59503970T patent/DE59503970D1/de not_active Expired - Fee Related
  • 1995-06-13 EP EP95810393A patent/EP0690103B1/fr not_active Expired - Lifetime
  • 1995-06-19 BR BR9502845A patent/BR9502845A/pt not_active Application Discontinuation
  • 1995-06-19 CN CN95107365A patent/CN1133322A/zh active Pending
  • 1995-06-20 KR KR1019950016324A patent/KR960001043A/ko not_active Application Discontinuation

Patent Citations (3)

Also Published As

Similar Documents

Legal Events